4,5-Bis-(trifluoromethylimino)-thiazolidines as fungicidal, insecticidal and acaricidal agents

ABSTRACT

Fungicidal, insecticidal and acaricidal compositions containing, and methods of combating fungi, insects and acarids using, novel 4,5-bis-(trifluoromethylimino)-thiazolidines of the formula   IN WHICH Z is R-N or   AND R, R&#39;&#39;, R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; each is hydrogen; alkyl, alkenyl or alkynyl with up to 8 carbon atoms optionally substituted by halogen, cyano, lower alkoxy or alkylmercapto; optionally lower-alkylsubstituted cycloalkyl; carbalkoxy; aralkyl with up to 2 carbon atoms in the alkyl moiety; aryl with up to 14 carbon atoms in the ring system, the aryl radicals optionally being substituted by halogen, cyano, nitro, lower alkyl, haloalkyl, lower alkoxy or alkylmercapto; a 5- to 7-membered heterocyclic ring or a radical which together with Z and the N-atom of the thiazolidine ring forms a further 5- to 7-membered ring, the heterocyclic rings optionally being substituted with halogen, cyano, nitro or lower alkyl, or being fused with a benzene ring which is optionally partially hydrogenated.

United States Patent Scholl et al.

[ Aug. 12, 1975 4,5-BIS-(TRIFLUOROMETHYLIMINO)- THIAZOLIDINES ASFUNGICIDAL, INSECTICIDAL AND ACARICIDAL AGENTS [73} Assignee: BayerAktiengesellschaft,

Leverkusen, Germany [22] Filed: Nov. 20, 1973 [2l] Appl. No.: 417,703

Related US. Application Data [63] Continuation-impart of Ser. No.206,158, Dec. 8,

[30] Foreign Application Priority Data Dec. 18, 1970 Germany 2062348[52] US. Cl 424/270; 260/306.7 [51] Int. Cl. A0ln 9/12; AOln 9/22 [58]Field of Search 424/270; 260/306.7

Ogden et al., J. Am. Chem. Soc., 89,, 5007-5011, (1967).

Primary Examiner\ D. Turner Attorney. Agent. or Firm-Burgess, Dinklage &Sprung [57] ABSTRACT Fungicidal, insecticidal and acaricidalcompositions containing, and methods of combating fungi, insects andacarids using, novel 4,5-bis-(trifluoromethylimino)-thiazolidines of theformula R, R, R" and R each is hydrogen; alkyl, alkenyl or alkynyl withup to 8 carbon atoms optionally substituted by halogen, cyano, loweralkoxy or alkylmercapto; optionally lower-alkyl-substituted cycloalkyl;carbalkoxy; aralkyl with up to 2 carbon atoms in the alkyl moiety; arylwith up to 14 carbon atoms in the ring system, the aryl radicalsoptionally being substituted by halogen, cyano, nitro, lower alkyl,haloalkyl, lower alkoxy or alkylmercapto; a 5- to 7-memberedheterocyclic ring or a radical which together with Z and the N-atom ofthe thiazolidine ring forms a further 5- to 7-membered ring, theheterocyclic rings optionally being substituted with halogen, cyano,nitro or lower alkyl, or being fused with a benzene ring which. isoptionally partially hydrogenated.

14 Claims, N0 Drawings about -50 to 120C to form4,5-bis-(trifluoromethylimino)-thiazolidines which are fungicidally,insecticidally and acaricidally active, with other and further objectsof the invention becoming apparent from a study of the withinspecification and accompanying examples.

The invention relates to the preparation of new 4,5-bis-trifluoromethylimino derivatives of thiazolidines of the generalformula S-eN-CF in which Zis RN=or \c a and,

R, R, R and R each is hydrogen; alkyl, alkenyl or i alkynyl with up to 8carbon atoms optionally substituted by halogemcyano, lower alkoxy oralkylmercapto; optionally lower-alkyl-substituted cy'cloalkyl;carbalkoxy; aralkyl with up to 2 carbon atoms in the alkyl moiety; arylwith up to 14 carbon atomsin the ring system, the aryl radicalsoptionally being substituted by halogen, cyano, nitro, lower alkyl,haloalkyl, lower alkoxy or alkylmercapto; a to- 7-membered heterocyclicring or a radical which together with Z and the N-atom of thethiazolidine ring forms a further 5- to 7- membered ring, theheterocyclic rings optionally being substituted with halogen, cyano,nitro or lower alkyl, or being fused with a benzene ring which isoptionally partially hydrogenated. In preparing the novel compounds, thethiol form of a thiourea or a thiocarboxylic acid amide having at leastone hydrogen atom on each urea or amide nitroat a temperature of about-50 to 120C Specifically a reactive isomeric form of thiocarboxylic acidamide in which Z and R' have the meanings stated above, is reacted withperfluoro-2,5-diazahexa-2,4 diene of the formula in the presence of ahydrogen fluoride acceptor at a temperature of about -50 to C.

It is very suprising that the above-mentioned compounds of the formula(II) produce, uniformly and with a satisfactory yield, the hithertounknown compounds of the formula (I) when reacted with perfluoro-2,5-diazahexa-2,4-diene of the formula (III). Furthermore, it is surprisingthat the compounds according to the invention possess fungicidal as wellas insecticidal and acaricidal effectiveness. The provision of this newclass of substances with interesting properties constitutes a technicaladvance.

If N,N-diphenyl-thiourea (which reacts in its thiol form) andperfluoro-2,5-diazaheXa-2,4-diene are used (III) as starting materials,and sodium fluoride as acid binding agent, the reaction course can berepresented by the following formula scheme:

(Ila) The thiocarboxylic acid amide derivatives or thiourea derivativesto be used as starting materials are, in their-isomeric form, definedgenerally by the above formula (II).

The radicals R, R, R and R' preferably are hydrogen; alkyl or alkenylwith up to 6 carbon atoms, optionally substituted by fluorine, chlorine,bromine and/or alkylmercapto; cyclopentyl or cyclohexyl carbomethoxy orcarboethoxy; benzyl or aryl with up to 10 carbon atoms in the ringsystem, the aromatic rings being optionally substituted by fluorine,chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl,chlorornethyl, trifluoromethyl, methoxy and/or methylmercapto; 5- or6-membered heterocyclic rings or radicals which together with Z and theN-atom of the thiazole ring form a 5- or 6-membered ring, theheterocyclic rings optionally being fused with a benzene ring which maybe partially hydrogenated. Most preferably Z is =N-R, R and R beinghydrogen, alkyl or aryl, or R and R' together form a heterocyclic ring.

The thiocarboxylic acid amide derivatives or thiourea derivatives to beused as starting materials which react with the'sulfu'r atom in thiolform as shown in the general, isomeric formula (II), are for themost-part known and can be prepared in generally knownmanner; they areobtained for example when thiocarbonic acid halides are reacted withammonia or primary amides; many thiourea derivatives can, furthennore,be prepared in known manner from primary amines and isothiocyanates. Thefollowing isothiocyanates may be mentioned: methylisothiocyanate,ethylisothiocyanate, butylisothiocyanate, phenylisothiocyanate,p-chlorophenylisothiocyanate. The perfluoro-2,5-diazahexa- 2,4-diene ofthe formula (III) to be used as starting material is known (J. Am.Chem.Soc. 89, 5007 (1967)).

As diluents, all inert organic solvents are suitable. Preferred solventsinclude hydrocarbons, such as benzine, benzene and toluene; nitriles,such as acetonitrile; and chlorinated hydrocarbons, such a methylenechloride, chloroform and chlorobenzene.

As acid binders, all customary acid-binding agents can be used. Theremay be mentioned alkali metal car bonates, alkali metal bicarbonates,tertiary amines, such as triethylamine, dimethylaniline. The alkalimetal fluorides, especially sodium fluoride, are preferred hydrogenfluoride acceptors.

The reaction temperatures can be varied within a fairly wide range. Ingeneral the reaction is carried out at about -50 to 120C, preferablyabout 30 to 90C.

in carrying out of the process according to the invention, for each moleof the compound of formula (II) there 'is generally used 1 mole ofperfluoro-2,5- diazahexa-2,4-diene of the formula (III); the alkalimetal fluoride is preferably used in excess, e.g. about 3 to 4 moles,but amounts lesser or greater than the stated proportions by up to 20per cent by weight can be used without substantial lowering of theyield. Expediently, the perfluoro- 2,5-diazahexa-2,4-diene is addeddropwise to a suspension of starting material, organic solvent andhydrogen fluoride acceptor. Filtration from the fluoride is theneffected, followed by concentration and recrystallization. Anothermethod of working up consists in adding water to the reaction mixtureand, optionally, recrystallizing the residue obtained.

The active compounds according to the invention exhibit a strongfungitoxic activity. In the concentrations necessary for the control offungi, they tend not to damage cultivated plants and they have a lowtoxicity to warmblooded animals. For these reasons, they'are suitablefor use as crop protection agents for the control of fungi. Fungitoxicagents in crop protection are used for the control of Archimycetes,Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfect).

The "active compounds according to the invention have a broad activityspectrum and can be applied against parasitary fungi which infectabove-the-ground parts of'plants or attack the plants from the soil, aswell as against seed-borne pathogenic agents.

The compounds possess a good activity against Fusicladium dendriticum,the causative organism of apple scab, against Phytophthora infestans,the causative organism of potato blight, and against Piricularia oryzae,the causative organism of rice blast.

The compounds according to the invention, however,

also act against other fungi which attack rice or other cultivatedplants, for example Mycosphaerella musicala,

Vefticillium alboatrum, Phialoph orea cinerescens and Fusarium species.7

The compounds according to the invention are distinguished by anextraordinarily high degree of activity and a very broad spectrumagainst phytopathogenic soil fungi and against seed-borne fun gal plantdiseases. They can be used preferably as soil treatment agents and seeddressings and are superior in this respect to customary commercialpreparations. The active compounds also possess an insecticidal andacaricidal effectiveness. The products may be used with success in cropprotection for the control of noxious sucking and biting insects,Diptera and mite (Acarina), as well as in the veterinaryand hygienefield; further, in the protection of stored products against amultiplicity of animal pests such as endopa'rasites and ectoparasites.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such'as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padithe pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus korschelti), the rosyapple aphid (Sappaphis mali), the mealy plum aphid (Hyalbpterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Caccina), for example the oleander scale (Aspidiotushederae) and the soft scale (Lecanium hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (Thysanoptera), such asHercinothrips femoralis, and bugs for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius) the bed bug (Cimexlectularius), the assassin but (Rhodnius prolixus) and Chagas bug(Triatoma infestans) and, further, cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus; and th like. 'a

In the case of the biting insects contemplated herein above allthere'shouldbe mentioned butterfly-caterpillars (Lepidoptera). such asthe diamond-back moth (Plutella maculipennis), the. gypsy moth(Lymantria dispar.) the brown-tail moth (Euproctis chrysor rhoea) andtent caterpillar Malacosma neustria); further, the'cabbage moth(Mamestra brassicae') and the cutworm (Agrotis segetum), the large whitebutterfly (Pieris brassicae), the small wintermoth (Cheimatobiabrumata),

the green oak tortrix moth (Tortrix viridana the fall armyworm (Laphygmafrugiperda) and cotton worm (Prodenia litura), the ermine moth(Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella)and greater wax moth (Galleria mellonella); and the like.

With the mites (Acari) there are classed, in particular, the spidermites (Tetranychidae) such as the twospotted spider mite (Tetranychustelarius.= Tetranychus althaeae or Tetranychus urticae) and the Europeanred mite (Paratetranychus pilosus Panonychus ulmi), gall mites, forexample the black currant gall mite (Eriophyes ribis) and tarsonemids,for example the broad mite (Hemitarsonemus latus) and the cyclamen mite(Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick(Ornithodorus moubata); and the like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents or extenders of the'typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powder dusting agents, granules, etc. These are preparedin known manner, for instance by extending the active compounds withconventional pesticide dispersible liquid diluent carriers and/0rdispersible solid carriers optionally with the use of carrier vehicleassistants, e.g. conventional pesticide surface-Active agents, includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxifiary solvents. The following may be chiefly considered for useas conventional carrier vehicles for this purpose; aerosol propellantswhich are gaseous at normal temperatures and pressures, such as freon;inert dispersible liquid diluent carriers including inert organicsolvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene,alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatichydrocarbons (e.g. chlorobenzenes), cycloalkanes (e.g. cyclohexane,etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc. alcohols (e.g.methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethersand esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g.ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides(e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water: aswell as inert dispersible finely divided solid carriers, such as groundnatural minerals (e.g. kaolins, alumina, silica, chalk, i.e., calciumcarbonate, talc, kiesel guhr, etc.) and ground synthetic minerals (e.g.highly dispersed silicic acid, silicates, e.g., alkali silicates, etc.);whereas the following may be chiefly considered for use as conventionalcarrier vehicle assistants, e.g., surface-active agents, for thispurpose:

emulsifying agents, such as non-ionic and/or anionic.

emulsifying agents (e.g. polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols,

alkyl sulfates, arkyl sulfonates, aryl sulfonates, etc., and especiallyalkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.);and/or dispersing agents, such as lignin, sulfite waste liquors, methylcellulose,

. etc.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95 percent, andpreferably 0.590 percent, by weight of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0001-l0 percent,preferably at least 0.5 percent weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (l) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible carrierliquid such as an inert organic solvent and/or water preferablyincluding a surfaceactive effective amount of a carrier vehicleassistant, e.g. a surface-active agent, such as an emulsifying agentand- /or a dispersing agent, and an amount of the active compound whichis effective for the purpose in question and which is generally betweenabout 01-95 percent, and preferably 0.5- percent by weight of themixture.

The active compounds can also be used in accordance with the well knownultra-low volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g/hectare, preferably 40to 600 g/hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95 percent by weight ofactive compound or even the percent active substance alone, e.g. about20-100 percent by weight of the active compound.

In the case of seed treatment, in general amounts of active compound of0.01 to 50 g, preferably 0.01 to 5 g, per kilogram of seed are appliedas a seed dressing.

For soil treatment, in general amounts of active compound of l to 500 g,preferably 10 to 200 g, are applied per cubic meter of soil. Theconcentrations of active compound in the ready-to-apply preparations mayvary very greatly. In general, they are from 0.0001 to 95 percent.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. fungi, insects andacarids, which comprise applying to at least one of correspondingly (a)such fungi, (b) such insects, (c) such acarids and (d) the correspondinghabitat thereof, i.e., the locus to be protected, a correspondinglycombative or toxic amount, i.e. a fungicidally, insecticidally, oracaricidally effective amount, of the particular active compound of theinvention alone or together with a carrier vehicle as noted above. Theinstant formulations or compositions are applied in the usual manner,for instance by spraying, atomizing, vaporizing, scattering, dusting,watering, sprinkling, pouring, via dressings, incrustations, and thelike.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding fungicidal and acaricidalactivity of such active compounds usable according to the presentinvention is illustrated, without limitation, by the following Examples.

EXAMPLE 1 Mycelium growth test 20 parts by weight agar-agar P s by gDemon? 200 parts by weight potato decoction 2 parts byweight Nazi-[P04'Fusidadium test (apple scab) (Protective) 5 pans by weight malt 0.3parts by weight 5 Solvent: 4.? parts by weight acetone 15 parts byweight dextrose Ca(NO EmulsifierI 0.3 parts by weight alkylarylpolyglycol ether Proportion of solvent to nutrient medium: P bfweight 2parts by weight acetone 100 parts by weight agar nutrient medium Theamount of active compound required for the de- 10 The amount of t vcompound required for the sired concentration of active compound in thenutrient sired Concentration of the active compound ht the medium ismixed with the stated amount of solvent. p y liquid is mixed with theStated amount of solvent, Th concentrate i th hl i d i h Stated and theconcentrate is diluted with the stated amount portion with the liquidnutrient medium which has been of Water Which Contains the Statedadditionscooled to 42C and is then poured into Petri dishes of o g ppSeedlings in the leaf Stage are 9 cm diameter. Control dishes to whichthe preparation p y with the p y liquid until pp g The h s t b add d arel Set up plants remain in a greenhouse for 24 hours at C and Whenthenutrient medium has cooled and solidified, at a lativ atmospherichumidity of 70 percent. They the dishes are in c lated with th ci of f iare then inoculated with an aqueous conidium suspent ted in the T bl d ib t d t b t 21C 20 sion of the apple scab causative organism (Fusicladium E l ati n i i d t ft 4-10 d d e d t dendriticum F uckel) andincubated for 18 hours in a huupon the speed of growth of the fungi.When evaluation midity Chamber at l8-20C and at a relative atmoiscarried out the radial growth of the mycelium on the ph h mi ity Of 100per ent. treated nutrient media is compared with the growth on Theplants are then again placed in a greenhouse for the control nutrientmedia.,ln the evaluation of the fun- 25 1 ays. gus growth, the followingcharacteristic values are 15 y te inoculation, the infection of theseedu ed; 7 lings is determined as a percentage of the untreated but 0no fungus growth also inoculated control plants. I

1 very strong inhibition of growth 0 percent means no infection; 100percent means 2 medium inhibition of growth that the infection isexactly as great as in the case of the 3 slight inhibition of. growthcontrol plants.

4 growth equal to that of untreated control. The active compounds, theconcentrations of the ac- The active compounds, their concentrations andthe tive compounds and the results can be seen from Table resultsobtained can be seen from Table l. 2:

3 w 2 2 Tablel 2 5. i3 5 5 mm r: '0? "33 92 8 L15 2585,2513 L 2- ea 5*;2H :2: :2 er 21:22 a 7 Pg; HQ! "4, HQ 0-H UG PKU O0 III1I '3 Activecompounds Concentration is 37; Q {3 E15 211i I18, 33. Ff :1 3 .9, 8. i3zfi a: 2 as :55. "at: 253182.; :2 PD!!! mo 05 rue FXNH mu zu OUCMUU EELCcn -r N'CF} 10 o o o o o t-cF l 9 I Table 2 t I Fusiclad'ium testProtective Active compound Infection as a percentage of the infection ofthe untreated control with a concentration of active compound (in ofknown) c p v r \t-s-cci (A) V 26 O 1 y I 20C and at a relativeatmospheric humidity of 70 percent. The tomato plants are theninoculated with an aqueous spore suspension of Phytophthora infestans.

35 The plants are brought into a moist chamber with an Water:

' The amount of the active compound required for the desiredconcentration of the active compound in the spray liquid is mixed withthe stated amount of solvent and the concentrate is diluted with thestated amount of water which contains the stated additions.

Young tomato plants (Bonny best) with 2-6 folliage leaves are sprayedwith the spray liquid until dripping atmospheric humidity of 100 percentand a temperature of 1820C.

After 5 days the infestation of the tomato plants is determined as apercentage of the untreated but likewise inoculated control plants: 0percent means no infestation; 100 percent means that the infestation isexactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults can be seen from the wet. The plants remain in a greenhouse for24 hours at 45 following Table:

Active compound Infection as a percentage of the infection oftheuntreated control with a concentration of active 'compound (in 7 of MI i a l Y u 7 y I C -NH-C- C Z-NH-C-S". j r S i i Q known)" m v ire Table 3 -Continued Infection 7 as percentage of the infection of theuntreated controlwith a concentration of active compound (in 7 of Ext-0PEXAMPLE 4 Agar plate test Test for fungitoxic effectiveness and breadthof the activity spectrum.

Solvent: Acetone Parts by weight: a) 1000 b) 100 and active compound hassolidified, test fungi from pure cultures are inoculated on to it insmall discs of 5 mm diameter. The Petri dishes remain at 20C. for 3 daysfor incubation.

After this time, the inhibiting action of the active compound on themycelium growth is determined in categories, taking into account theuntreated control. 0 means no mycelium growth, either on the treatedsubstrate or on the inoculum; the symbol means mycelium growth on theinoculum only, no spread to the treated substrate; and the symbol meansmycelium growth from the inoculum on to the treated substrate similar tothe spread of the untreated substrate of the control.

The active compounds, the concentration of the active compounds, thetest fungi and the inhibition effects achieved can be seen from thefollowing Table 4.

Table v v s a 4'1 w Agar plate test 33 3 g g 1 .e c 0 r4 a o .e E I 5 HHH :1 H :I 4- E E E E :3 EH Active compound Concentration of v "a: at;g}; :3. if. 3 a 3 5 ,3 active compound in o .8 w e r-1 0 o o n o H na:the substrate in I: :3 22 371i 513 35 3i i 3.37,.

PK/litre 83 $51-$31 E53 5.8 fi :35 'lfia I I l CH -NHCS 2 (B) 10 E 'b) OS (known) i 3 g l 0 N (l) b) 100 0 v 0 O O Fat-m i i: -cr N 3 (3) a) 10O O O s-=n cr by 0 o o o o o o o.

3-N-CF Clif 5 (5) a) o o 0 0 0 0 0 t-CF 100 o 0 Q o O O O O EXAMPLE 5Seed dressing test/bunt of wheat (seed-home mycosis) To produce asuitable dry dressing, the active compound is extended with a mixture ofequal partsby weight of talc and kieselguhr to give a finely powderedTable 5 Seed dressing test bunt oi wheat Active compounds Concentrationof Applied Spore active compound amount of germinain the dressingdressing tion in i by weight in g/kg in iv seed non dressed 10 H filli3.2 (B) CH NHC 1 g 10 1 5 30 1 0.05 (known) N--.N--0I- 10 1 0.000 1) 3o 10.000 S-=N-0F inf-raga; i F 2 10 1' 0.005 itc 3 3o 1 0.005

FL N- CF 3 (3) 1o i 1 0.05

\5 N CF3 30 l q. 300

=N-CF c 4; (5) 10 1 0'0 3 Y :ar-OF 05 1 5 3 l 0. 000

mixture with the desired concentration of the active EXAMPLE 6 compound.

Wheat seed is contaminated with 5 g of the chlamydo Seed dressmg P; ofbarley (Seed borne spores of Tilletia caries per kg of seed. To apply.the dressing, the seed is shaken with the dressing in a closed glassflask. The seed, on moist loam under a cover of a layer of muslin and 2cm of moderately moist compost soil, is exposed to optimum germinationconditions for the spores for 10 days at 10C in a refrigerator.

The germination of the spores on the wheat grains, each of which iscontaminated with about 100,000 spores, is subsequently determinedmicroscopically.

To produce a suitable dry dressing, the active compound is extended witha mixture of equal parts by weight of talc and kieselguhr to give afinely powdered mixture with the desired concentration of activecompound.

To apply the dressing, barley seed, which is naturally infested byHelminthosporium gramineum, is shaken with the dressing in a closedglass flask. The seed, on moist filter paper discs in closed Petridishes, is exposed to a temperature of 4C for 10 days in a refrigerator.The germination of the barley, and possibly also of the fungus spores,is thereby initiated. Two batches of 50 grains of the pregerminatedbarley are subsequently sown 2 cm deep in Fruhstorfer standard soil andculti-v vated in a greenhouse at temperatures of about 18C in' seedboxes which are exposed to light for 16 hours daily. The typicalsymptoms of the stripe disease develop within 3 to 4 weeks.

After this time, the number of diseased plants is de.

Table 6 1 pound, the active compound is extended with talc to a contentof 5 percent and subsequently with quartz sand to a content of 0.5percent of active compound.

The preparation of the active compound is uniformly mixedwith-Fruhstorfer standard soil, Which has first been sterilized and theninoculated with pure cultures of the test fungi.

The soil is filled into 5 pots, each of which is sown 10 seeds of thehost plants. The pots are placed in agreenhouse at the statedtemperatures and kept normally moist.

3 weeks after sowing, the number of healthy plants is determined as apercentage of the number of seeds sown. 0 percent means that no healthyplants have grown; 100 percent means that healthy plants have resultedfrom all the seeds.

Seed dressing test/stripe disease of barley Number of stripe Activecompound Concentration of Applied active compound amount of lediseusedin the dressing dressing plants as a in fi 'by weight in g/kg percentagecf seed the total number l of emerged plants non-dressed 5 x 23.6

in --=-N-C-F t .(3) '30 2 .1

-.-N-CF (m N N-CCF g e 3 -CF 3O 2 10.1

EXAMPLE 7 5 The active compounds, the concentrations of the ac- Soiltreating agent test/soil-borne mycoses tive compounds in the soil, thetest fungi, host plants,

greenhouse temperatures and the results obtained can be seen from Table7:

Table 7 Test fungi:

Fusarium cuL'norum EXAMPLE 8 Tetranychus test phosphoric acid esterresistant strain Solvent: 3 parts by weight dimethyl formamideEmulsifier: 1 part by weight alkylarylpolyglycol ether To produce asuitable preparation of active compound, 1 part by weight of the activecompound is mixed with the stated amount of solvent containing thestated amount of emulsifier and the concentrate so obtained is dilutedwith water to the desired concentration.

Host plant: Pea

Tem erature range: 22-25 v Active compounds Concentration of activecompound in mg/liter soil Fruhstorfer standard soil,sterilized untreatedFruhstorfer standard soil,steri1ized untreated 2O li r-l l g 1'00 2k'nciwn) s N-CF 'CH fN- r Pat-CF 1Q0 of approximately 10-30 cm., aresprayed with the preparation of the active compound until dripping wet.These bean plants are heavily infested with spider mites (Tetranychusurticae) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:percent that all the spider mites are killed whereas 0 percent meansthat none of the spider mites are killed.

The active compounds, the concentration of the ac tive compounds, theevaluation times and the results Bean plantsiPh aseolus vulgaris), whichhave a height 65 can be seen from the following Table 8.

Active compounds Concentration of active compound Degree of destructionin 9 in 94 after 8 days on -c1 =m@CO-NH-CH 3 H 0.2 v 100 I I 0.02 1 0(known) (C) I 2;: l' I. 3 0.2 100 (4) 0.02 {109 I:=N-CF, 0.002 90 -CF ts n-cr EXAMPLE 9 aration of the active compound until dripping wet.-

Temmydms mt carbamate resismt Swain 5 These bean plants are'heavilyinfested with spider mites m by weight acetone (Tetranychus urtzcae) inallstages of development.

Emulsifier: l' an by weight alkylaryl polyglycol ether After thespecified periods of time, the effectiveness To produce a suitablepreparation of active comof the preparation of active compound isdetermined pound, 1 part by weight of the active compound is by countingthe dead mites. The degree of destruction mixed with the stated amountof solvent containing the 40 thus obtained is expressed as a percentage:100 percent stated amount of emulsifier and the concentrate so obmeansthat all the spider mites are killed whereas'O pertained is diluted withwater to the desired concentracent means that none of the spider mitesare killed. tion. The activecompounds, the concentrations of the ac-Bean plants (Phaseolus vulgaris), which have a height tive compounds,the evaluation times and the results of'approximately 10-30 cm., aresprayed with the prepcan beseen from the following Table I0.

( plant-damaging mites) Active compounds Concentration of Degree ofdestrucactive compound tion in flatter in ,1 t 8 days p ,9- 0x 8 O-C-N'H-'-CH (E) v p Oil I o IN" i.l

(known) EXAMPLE 10 Phaedon larvae test Solvent: 3 parts by weightdimethyl formamide Emulsifier: 1 part by weight alkylaryl polyglycolether To produce a suitable preparation of active compound, 1 part byweight of the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dripping wet and then infested with mustardbeetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100 percent means that all the beetle larvaeare killed. percent means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, thetimes of evaluation and the results can be seen from the following TableII.

Table (plant-damaging insects) Phaedon larvae test Active compoundsConcentration of active compound afterwards effected for 2 hours at roomtemperature followed by addition of 1 liter of water to the reactionmixture and then filtration. After recrystallization of the residue fromacetone there are obtained 31 g of the compound of the above formula ofm.p. l202C.

Yield: 92 percent of theory.

EXAMPLE l2 Analogously with Example 12, with thiourea instead ofZ-mercapto-benzimidazole there are obtained, after' working up with 1liter of water, 2] g of 2-imino-4,5-bis-trifluoromethylimino-thiazolidine of mp. 150C (with decomposition).Yield: 80 percent of theory.

Degree of destruction in The following further examples are set forth toillustrate, without limitation, the process for producing the activecompounds according to the present invention.

EXAMPL E l 1 To 15 g (0.1 mole) of Z-mercapto-benzimidazole and 65 inafter 3 davs (knownl N\ L (a) 0.02 3

-s-'-+ N-CF3 i lt-0P :fl-CF; (5) 0.2 1C0 EXAMPLE 1 3 IV-0P Analogouslywith Example 12 with N,N'- ethylenethiourea there are obtained 23 g ofthe above compound of m.p. 8687C (from ether/pentane). Yield: 79 percentof theory.

Analogously with Example A 12, with N,N'- diphenylthiourea there areobtained 35 g of the above compound of m.p. ll8119C* (from methanol).

*1 Yield: 84 percent of theory.

EXAMPLE 1 5 Analogously withExample l2, \m'th N-phenyl-N' methylthioureathere are obtained g of the above compound of m.p. l68169C. Yield: 80percent of theory.

diisopropylthiourea there is obtained the compound of the above formulaof m.p. 46C. Yield: 80 percent of theory.

EXAMPLE 1 7 Analogously with Example. 12, with N-naphthyl-N'- methylthiourea there'is obtained the compound of the above formula of m.p.19019lC. Yield: 81 percent of theory.

EXAMPLE l8 Analogously with Example 12, 'withN-p-nitrophenyl-N-methylthiourea there is obtained the com- Yield:" 78"percent of theory.

pound of the above formula of m.p. 174 to EXAMPLE l9 S fill-C1 5 em I 1N-CF 9) Cl Analogously, with Example 12, with N-p-chlorophenyl-N-methylthiourea there is obtained the compound of the above formula of m.p. 212to 213C. Yield: 77 percent of theory.

Other compounds which can be similarly prepared include: 1

Compound X m.p.

25 FCH 92 26 3-cH A 102 27 h-C H O 97 28 -l-Cl 100-401 R,-R',R" and Reach is hydrogen; alkyl, alkenyl or alkynyl with up to 8 carbon atomsoptionally substituted by halogen, cyano, lower alkoxy or alkylmercaptoof up to 3 carbon atoms; cyclopentyl or cyclohexyl optionallysubstituted with alkyl of up to 3 carbon atoms, carbalkoxy having up to8 carbon atoms in the alkoxy group; phenylalkyl or naphthylalkyl with upto 2 carbon atoms in the alkyl moiety; or phenyl or naphthyl radicalsoptionally being substituted by halogen, cyano, nitro, lower alkyl of upto 3 carbon atoms, haloalkyl of up to 8 carbon atoms, lower alkoxy oralkylmercapto of up to 3 carbon atoms.

2. The method according to claim 1 in which Z is =N-R, and'R and R' arehydrogen; alkyl or alkenyl with up to 6 carbon atoms, optionallysubstituted by fluorine, chlorine, bromine or alkylmercapto of up to 3carbon atoms; cyclopentylor cyclohexyl; carbomethoxy or carboethoxy;benzyl; or phenyl or naphthyl optionallysubstituted by fluorine,chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, chloromethyl,'trifluoromethyl, methoxy or methylmercapto.

3. The method according to claim 2, in which R and R are hydrogen, alkylor phenyl.

4. The method according to claim 1 wherein such compound has the formula5. Themethod .accordingto claim 4 wherein the compound is applied toacarids or an acarid habitat.

6. The method according to claim 4 wherein the compound is applied tofungi or a fungus habitat.

7. The method according to claim 1 wherein such compound has the formula8. The method according to claim 7 wherein the compound is applied tofungi or a fungus habitat.

9. The method according to claim 1 wherein such compound has the formula10. The method according to claim 9 wherein the compound is applied tofungi or a fungus habitat.

11. The method according to claim 1 wherein such compound has theformula 12. A fungicidal, insecticidal or acaricidal compositioncomprising a fungicidally, insecticidally or acaricidally effectiveamount of a compound of the formula I =N-0F II I in which Z is R--N= orand R, R, R and R each is hydrogen; alkyl, alkenyl or alkynyl with up to8 carbon atoms optionally substituted by halogen, cyano, lower alkoxy oralkylmercapto of up to 3 carbon atoms, cyclopentyl or cyclohexyloptionally substituted with alkyl of up to 3 carbon atoms; carbalkoxyhaving up to 8 carbon atoms in the alkoxy group; phenylalkyl ornaphthylalkyl with up to 2 carbon atoms in the alkyl moiety; or phenylor naphthyl radicals optionally being substituted by halogen, cyano,nitro, lower alkyl of up to 3 carbon atoms, haloalkyl of up to 8 carbonatoms, lower alkoxy or alkylmercapto of up to 3 carbon atoms inadmixture with a diluent.

"27 v .l 13. The composition according to claim 12 vheiein said compoundis:

14. The composition according to claim 12 wherein said compound is

1. A METHOD OF COMBATING FUNGI, INSECTS OR ACARIDS WHICH COMPRISESAPPLYING TO SUCH FUNGI, ACARIDS OR A HABITAT THEREOF A FUNGICIDALLY,INSECTICIDALLY OR ACARICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THEFORMULA
 2. The method according to claim 1 in which Z is N-R, and R andR'''''' are hydrogen; alkyl or alkenyl with up to 6 carbon atoms,optionally substituted by fluorine, chlorine, bromine or alkylmercaptoof up to 3 carbon atoms; cyclopentyl or cyclohexyl; carbomethoxy orcarboethoxy; benzyl; or phenyl or naphthyl optionally substituted byfluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl,chloromethyl, trifluoromethyl, methoxy or methylmercapto.
 3. The methodaccording to claim 2, in which R and R'''''' are hydrogen, alkyl orphenyl.
 4. The method according to claim 1 wherein such compound has theformula
 5. The method according to claim 4 wherein the compound isapplied to acarids or an acarid habitat.
 6. The method according toclaim 4 wherein the compound is applied to fungi or a fungus habitat. 7.The method according to claim 1 wherein such compound has the formula 8.The method according to claim 7 wherein the compound is applied to fungior a fungus habitat.
 9. The method according to claim 1 wherein suchcompound has the formula
 10. The method according to claim 9 wherein thecompounD is applied to fungi or a fungus habitat.
 11. The methodaccording to claim 1 wherein such compound has the formula
 12. Afungicidal, insecticidal or acaricidal composition comprising afungicidally, insecticidally or acaricidally effective amount of acompound of the formula
 13. The composition according to claim 12wherein said compound is:
 14. The composition according to claim 12wherein said compound is